Sodium exo-cis-1,4-endoxo-1-substituted cyclohex-5-ene-2,3-dicarboxylate compounds

ABSTRACT

THE USE OF EXO-CIS-1,4-ENDOXO-ALICYCLIC-2,3-DICARBOXYLATES SUCH AS SODIUM EXO-CIS-1,4-ENDOXOCYCLOHEXENE-2,3DICARBOXYLATE AND DERIVATIVES THEREOF AS BUILDERS IN DETERGENT COMPOSITIONS.

United States Patent Office Patented May 29, 1973 3,736,339 SODIUMEXO-CIS 1,4-ENDOXO-1-SUBSTITUTED CYCLOHEX 5-ENE-2,3-DICARBOXYLATE COM-ABSTRACT OF THE DISCLOSURE The use ofexo-cis-1,4-endoxo-alicyclic-2,3-dicarboxylates such as sodiumexo-cis-1,4-endoXocyclohexene-2,3- dicarboxylate and derivatives thereofas builders in detergent compositions.

BACKGROUND OF THE INVENTION Field of the invention Detergentcompositions containing detergent builders.

Background In recent years, studies have been conducted concerning theproblems of eutrophication. Eutrophication can be defined as a naturalprocess of enrichment of waters with nutrients, such as phosphorus andnitrogen, at a slow rate. Eutrophication can be detrimental, since itmay cause increased algal growth and algal scums which are unaesthetic,odorous, distasteful and often clog filters of water treatment plants.

It has been postulated that various human activities have acceleratedthe process. Contributing factors in the eutrophication of lakes,streams and estuaries are natural runotf, agricultural drainage, groundwater, precipitation, sewage and Waste efiluents. Although there is nopresent adequate proof, it has been postulated that thephosphorus-containing builders present in detergent compositions can bea factor in eutrophication, and therefore any substitutes which do notcontain phosphorus may decrease to some extent the eutrophicationproblem. Thus, those skilled in the art have expended a great deal oftime and money to find suitable materials to reduce or replace theexisting phosphate builders in detergent compositions. However, mostbuilders which have been discovered to date have been unsatisfactory forone or many possible reasons and are normally less eflicient than theexisting phosphorus builder materials.

The exo-cis-1,4-endoxo-alicyclic (or cycloaliphatic)- 2,3-dicarboxy1atesand derivatives thereof used as builders in accordance with the presentinvention not only permit the reduction or replacement of existingphosphate and nitrogen-containing builders in detergent compositions,but in addition, aiford a detergent composition containing a builderwhich is biodegradable.

SUMMARY OF THE INVENTION It is an object of the present invention toprovide detergent compositions containing builder compounds which arefree of phosphorus and are efficient detergent builders.

It is another object of the invention to provide compositions containingbuilder compounds which can be synthesized from low most raw materialsat reasonable prices.

Still another object of the present invention is to provide new organiccompounds which may be utilized as builders in detergent compositions.

DESCRIPTION OF THE INVENTION It has now been discovered that certainoxygen-bridged bicyclic or tricyclic diand polycarboxylates can serve aseffective detergent builders in detergent compositions.

The builders employed in accordance with the present invention can begenerally described as exo-cis-1,4-endoxo-alicyclic-2,3-dicarboxylatewater-soluble salts having the general formula:

Formula I o o OM Z Y COOM wherein Z is a bivalent radical consisting of1-4 carbon atoms wherein said radical may contain additionalsubstituents selected from the group consisting of halogen, hydroxyl,phenylene, carboxyalkyl, arylalkyl, alkoxyalkyl, oxoalkyl orhydroxyalkyl containing 1-3 carbon atoms in the alkyl chain; at leastone of Y is hydrogen and the other is selected from the group consistingof hydrogen, chloro or lower alkyl containing 1-3 carbon atoms; and Xand X are independently selected from the group consisting of hydrogen,hydroxymethyl, fi-cyanoethyl, ,B-cyanoethoxymethyl, carboxyethoxymethyl,dimethoxymethyl, diethoxymethyl, dioxolanyl and carboxyloweralkylcontaining 1-3 carbon atoms; and M is hydrogen or a cation selected fromthe group consisting of alkali metals, ammonium and substituted ammoniumradicals.

The term cis as used herein refers to the fact that both carboxylategroups are on the same side of the ring.

The term exo as used herein refers to the fact that the carboxylategroups are on the same side of the alicyclic ring as the oxygen bridge.

Thus the compounds of the present invention may be bior tricycliccompounds embracing in their basic structure a hydroaromatic oraliphatic ring wherein (in reference to Formula I), the 1-4 positionring carbon atoms are bridged with an oxygen atom and carboxylate saltfunctions are attached to the 2 and 3 position carbon atoms. In the caseof tricarboxylate salts, the third carboxylate group is attached as partof substituent in the 1 position.

The compounds employed in the present invention are for the most partknown or can be prepared in accordance with procedures well known in theart. For example, Diels-Alder reactions, which yield some of the typesof compounds of interest, may be conducted in accordance with theteaching of Kloetzel on pages 1-60 of Organic Reactions, volume 4, JohnWiley and Son, Inc. (1948), or the teachings of Holmes on pp. 60-174 ofthe same volume or according to the method of Woodward and Baer (I. Am.Chem. Soc., 70, 1161 (1948), or the teachings of US. Pat. No. 3,047,433.The preparation of other compounds described in the present inventionwill be apparent from the discussion hereinafter.

As may be appreciated, the aforementioned compounds may exist in severalisomeric forms. As may be further appreciated, compounds of the presentinvention may be employed as builders in detergent compositions in theform of the anhydride, the free acid or a water-soluble salt thereof. Ofcourse, when the anhydride or free acid form is employed, there must bepresent in the detergent composition sufficient alkali or neutralizingagents such as sodium hydroxide or carbonate to form the correspondingsalt in situ. Accordingly in the preferred embodiment of the invention,it is most desirable to use theexo-cis-l,4-endoxo-alicylic-2,3-dicarboxylates in the form of theirWater soluble salts and preferably the alkali metal ('K, Na), ammoniumand substituted ammonium salts such as the mono-di andtriethanolammonium, tetramethylammonium, methylammonium and morpholiniumsalts.

Laboratory studies have indicated that in regard to detergency buildingcharacteristics, best results are obtained by utilization of the morestable exo-cis isomer, although mixtures containing both endo andexo-cis isomers are useful, since a substantial proportion of theendo-cis isomer contained in the mixture is capable of isomerizing tothe exo isomer.

Laboratory evidence further indicates that the unique building activityof the compound of Formula I appears to be related to the particularspatial relationship of the oxygen to the dicarboxylate functions, i.e.,that the 2,3- carboxylate groups are cis to one another and that theyalso are on the same side of the alicyclic ring as the oxygen bridge,i.e., in the exo position.

Notwithstanding the activity exhibited by the compounds of the presentinvention broadly, certain of the compounds of Formula I exhibitoutstanding superior properties as detergent builders. These includecompounds of the type wherein Z is a bivalent radical of 2 carbon atomsand thus embrace compounds including in their structures a basicsix-membered ring which is hydroaliphatic or hydroaromatic but alsocontains an oxygen bridge. Within this class, of particular note are:

(1) disodium exo-cis-1,4-endoxo-cyclohexene-2,3-dicarboxylate;

(2) disodium exo-cis-l,4-endoxo-cyclohexane-2,3-dicarboxylate;

(3) disodium exo-cis-l,4-endoxo-l-diethoxymethyl-Acyclohexene-2,3-dicarboxylate;

(4) disodium exo-cis-1,4-endoxo-1-(2-rn-dioxanyl)-Acyclohexene-2,3-dicarboxylate;

(5) disodium exo-cis-l,4-endoxo-1-hydroxymethyl-Acyclohexene-2,B-dicarboxylate;

(6) disodium exo-cis-l,4 endoxo-1-[(fi-cyanoethoxy) methyl]-A-cyclohexene-2,3-dicarboxylate;

(7) trisodium exo-cis-1,4-endoxo-l-(B-carboxyethoxymethyl)-A-cyclohexene-2,3-dicarboxylate.

According to the present invention, excellent cleaning results can beobtained by using the builders described above with a wide range ofdetergent surface active materials and mixtures thereof in solid orliquid form. The builders can be used singularly, in combination witheach other as the sole builder in the detergent composition or incombination with other well-known detergent builders such as sodiumnitrilotriacetate, sodium ethylenedia-minetetraacetate, sodiumtripolyphosphate, sodium and potassium pyrophosphate, and sodiumpolyacrylate, sodium carbonate, sodium silicate and the like.

In the detergent compositions of the present invention, the onlyessential ingredients are the detergent surface active material and thebuilder. The weight percent of the builder present in the detergentcomposition will range from about 5 to about 90% and preferably fromabout 210 to about 60% and more preferably 35-50% by weight of the totalweight of the composition. When expressed as a weight ratio of builderto surfactant, the builders used in the instant invention will generallybe present in a ratio of about 1:10 to about 10:1, and preferably 2:1-5:1 depending on the end use or whether a heavy-duty or light-dutydetergent is desired.

Similarly, in detergent compositions suitable for Washing dishes inmechanical dishwashers, the ratio of builder to detergent may be as highas 50:1.

The detergent surface "active compounds which can be used in thecompositions of this invention include anionic, nonionic, zwitterionic,ampholytic detergent compounds and mixtures thereof. These suitablesubstances are outlined at length below.

(a) Anionic detergent compositions which can be used in the compositionsof this invention include both soap and non-soap detergent compounds.Examples of suitable soaps are the sodium, potassium, ammonium andalkylolammonium salts of higher fatty acids (C -C Particularly usefulare the sodium or potassium salts of the mixtures of fatty acids derivedfrom coconut oil and tallow, i.e., sodium or potassium tallow andcoconut soap and tall oil. Examples of anionic organic non-soapdetergent compounds are the water soluble salts, alkali metal salts oforganic sulfuric reaction products having in their molecular structurean alkyl radical containing from about 8 to about 22 carbon atoms and aradical selected from the group consisting. of sulfonic acid andsulfuric acid ester radicals. (Included in the term alkyl is the alkylportion of higher acyl radicals.) Important examples of the syntheticdetergents which form a part of the compositions of the presentinvention are the sodium or potassium alkyl sulfates especially thoseobtained by sulfating the higher alcohols (C -C carbon atoms) producedby reducing the glycerides of tallow or coconut oil; sodium or potassiumalkyl benzene-sulfonates in which the alkyl group contains from about 9to about 20 carbon atoms and in which the benzene ring is attached tothe alkyl chain at either the one position or at the secondary positionssuch as in sodium linear alkyl (C C secondary benzene sulfonate, sodiump-(Z-dodecyl) benzene sulfonate, sodium p-(2-octadccyl)benzenesulfonate, sodium p- (3-dodecyl)benzene sulfonate and3-phenyldodecanesulfonate; sodium alkyl glyceryl ether sulfonates,especially those ethers of the higher alcohols derived from tallowcoconut oil and synthetic alcohols derived from petroleum; sodiumcoconut oil fatty acid monoglyceride sulfates and sulfonates; sodium orpotassium salts of sulfuric acid esters of the reaction product of onemole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols)and about 1 to 6 moles of ethylene oxide per molecule and in which thealkyl radicals contain about 9 to about 18 carbon atoms; the reactionproduct of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil; sodium or potassium salts of fatty acid amides ofmethyl taurine in which the fatty acids, for example, are derived fromcoconut; alkane sulfonates such as those derived by reactingalpha-olefins containing 8 to 20 carbon atoms with sodium bisulfite andthose derived by reacting parafiins with S0 and C1 and then hydrolyzingwith a base to produce a random sulfonate; alpha-olefin sulfonates suchas those derived by reacting alpha-olefins with $0 and then neutralizingthe reaction product; and others known in the art.

(b) Nonionic synthetic detergents may be broadly de fined as compoundswhich do not ionize in water solution. For example, a well-known classof nonionic synthetic detergents is made available on the market underthe trade name of Pluronic. These compounds are formed by condensingethylene oxide with an hydrophobic base formed by the condensation ofpropylene oxide with propylene glycol. The hydrophobic portion of themolecule which, of course, exhibits water insolubility has a molecularweight of from about 1,500 to 1,800. The addition of polyoxyethyleneradicals to this hydrophobic portion tends to increase the watersolubility of the molecule as a whole and the liquid character of theproduct is retained up to the point where polyoxyethylene content isabout 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkylphenols, e.g., thecondensation products of alkylphenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to 5 to 25 moles of ethylene oxide per mole ofalkylphenols. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, disobutylene, octene, dodecene, or nonene,for example.

(2) Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide andethylenediamine. For example, compounds containing from about 40% toabout 80% polyoxyethylene by weight and having a molecular weight offrom about 5,000 to about 11,000 resulting from the reaction of ethyleneoxide groups with a hydrophobic base constituted of the reaction productof ethylene diamine and excess propylene oxide, said hydrophobic basehaving a molecular weight of the order of 2,500 to 3,000 aresatisfactory.

(3) The condensation product of aliphatic alcohols (primary orsecondary) having from 8 to 18 carbon atoms, in either straight chain orbranched cham configuration, with ethylene oxide, e.g., a coconutalcoholethylene oxide condensate having from 6 to 30 moles of ethyleneoxide per mole of coconut alcohol, the coconut alcohol fraction havingfrom 10 to 14 carbon atoms or a random secondary C C alcohol-ethyleneoxide condensate having 6 to 15 moles of ethylene oxide per mole ofalcohol.

(4) Long chain tertiary amine oxides corresponding to the followinggeneral formula, R R R N O, wherem R is an alkyl radical of from about 8to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethylradicals. The arrow in the formula is a conventional representation of asemi-polar bond. Examples of amme oxides suitable for use in thisinvention include dimethyldodecylamine oxide, dimethyloctylamine oxide,dimethyldecylamine oxide, dimethyltetradecylamine oxide and d1-methylhexadecylam ine oxide, N-bis(hydroxyethyl) dodecylamine oxide.

Long chain tertiary phosphine oxldes corresponding to the followingformula RRRP- O, wherein is an alkyl, alkenyl or monohydroxyalkylradical ranging from to 18 carbon atoms in chain length and R and R" areeach alkyl or monohydroxyalkyl groups contaming from 1 to 3 carbonatoms. The arrow in the formula is a conventional representation of asemi-polar bond. Examples of suitable phosphine oxides are:

dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide,ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide,dimethylstearylphosphinc oxide, cetylethylpropylphosphine oxide,diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide,bis(hydroxymethyl)dodecylphosphine ox de,bis(2-hydroxyethyl)dodecylphosphine oxide,2-hydroxypropylmethyltetradecylphosphine oxide, dimethyloleylphosphineoxide, and dimethyl-Z-hydroxydodecylphosphme oxide.

(6) Dialkyl sulfoxides corresponding to the following formula, RR'S O,wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical oran all yl or betaor gamma-monohydroxyalkyl radical containlng one or twoother oxygen atoms in the chain, the R groups ranging from 10 to 18carbon atoms in chain length, and wherein R is methyl, ethyl oralltylol. Examples of suitable sulfoxide compounds are:

dodecyl methyl sulfoxide,

tetradecyl methyl sulfoxide,

3-hydroxytn'decyl methyl sulfoxide Z-hydroxydodecyl methyl sulfoxide3-hydroxy-4-decyloxybutyl methyl sulfoxide, 3-hydroXy-4-dodecylcoxybutylmethyl sulfoxide, 2-hydroxy-3-decyloxypropyl methyl sulfoxide,Z-hydroxy-3-dodecyloxypropyl methyl sulfoxide, dodecyl ethyl sulfoxide,

Z-hydroxydodecyl ethyl sulfoxide, and dodecyl-Z-hydroxy ethyl sulfoxide.

(c) Ampholytic synthetic detergents can be broadly described asderivatives of aliphatic secondary and tertiary amines, in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to 18 carbon atoms andone contains an anionic water solubilizing group. Examples of compoundsfalling within this definition are sodium-3-dodecylaminopropionate andsodium-3-dodecylaminopropanesulfonate and sodium N-Z-hydroxydodecyl-N-methyl-taurate.

(d) Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium compounds, sulfoniumcompounds and phosphoniurn compounds in which the aliphatic radical maybe straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group. Examples of compounds fallingwithin this definition are 3(N,N-dimethyl-N-hexadecylamrnonio)propane-l-sulfonate, 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate, 3(dodecylmethylsulfonium) propane sulfonate, and3-(cetylmethylphosphonium) ethane sulfonate.

In addition to the essential ingredients in the detergent composition,other optional ingredients may also be added. Examples of the optionalingredients are perfumes, colorants, fabric softening agents,fungicides, germicides, enzymes, fluorescent dyes, antiredepositionagents, hydrotropes and in the case of liquid compositions, opacifiersand organic solvents. Other ingredients such as bleaches, i.e., sodiumperborate with or without activators and inorganic salts such as sodiumcarbonate, sodium bicarbonate, sodium sulfate, sodium chloride andsodium silicate may also be present.

The detergent compositions of the present invention can be utilized inwashing solutions over a pH range of from about 7-12 and more preferably9-11 when used as laundry and dishwashing compositions.

In addition to the unique detergent building properties the compoundsused in the present invention when employed in the free acid or aspartly neutralized salts, are valuable in metal cleaning compositionsunder pH conditions of about 2 to about 5. Such compositions maytherefore contain in addition to the surfactant all standard cleaningabrasives.

Still another embodiment of the present invention is the use ofanhydrides of Formula I in conjunction with inorganic persalts such assodium perborate and sodium percarbonate. It is believed that thehydrogen peroxide released when such persalts are dissolved in waterreacts with the anhydrides to form peracids capable of bleaching. Theperacids are ultimately converted to the dicarboxylate salts of FormulaI and can then function as detergent builders. Thus,the anhydrides canbe said to be dual-functioning, i.e., they are both bleach precursors inthat they can form peracids and detergent builder precursors in thatthey can form dicarboxylate salts of Formula I.

It is intended to cover'all changes and modifications of the preferredembodiments of the invention, herein chosen for the purpose ofillustration, which do not constitute departures from the spirit andscope of the invention.

EXAMPLE 1 Disodium exo-cis-1,4-endoxo-cyclohexane- 2,3-dicarboxylate Toa Parr low pressure hydrogenator were added 50 gm. ofexo-cis-1,4-endoxo-A -cyclohexene-2,3-dicarboxylic anhydride dissolvedin ml. of anhydrous acetone and 0.6 gm. of 10% palladium on charcoalwhich was then pressurized to 40-50 p.s.i. with hydrogen. The apparatuswas allowed to shake for a period of two hours whereupon hydrogenationwas terminated and the contents of the bomb removed and filtered. Uponcooling the filtered solution to about 70 C.,exo-cis-1,4-'endoxocyclohexane-2,3-dicarboxylic anhydride (25.7 gm.) inthe form of a white crystalline precipitate was obtained and collectedby suction filtration. The anhydride was then dissolved in 400 ml. ofhot water to which 16 gm. (0.15 mole) of sodium carbonate were added andthe resulting solution Was evaporated to dryness to yield disodiumexocis-1,4-endxo-cyclohexane-2,3-dicarboxylate.

The corresponding ammonium and substituted ammonium salts are preparedby treating the anhydride with dilute ammonium hydroxide or an aqueoussolution of the appropriately substituted amine. Correspondingmono-salts are prepared by employing half the stoichiometric quantitiesrequired for producing the disalt.

EXAMPLE 2 Exo-cis- 1,4-endox0- 1- B-cyanoethoxy methyl] -Acyclohexene-2,3-dicarboxylic anhydride A mixture of 15 gm. (0.1 mole) offi-cyanoethylfurfuryl ether and 9.8 gm. (0.1 mole) of maleioanhydride in100 ml. of ether were added to a 250 ml. onenecked, round bottomed flaskfitted with a reflux con denser and drying tube. The mixture was thenstirred for one day and allowed to stand for 2 /2 days, whereupon theether layer from the resulting two-phase mixture was separated andevaporated without heat to yield a. viscous material, which uponextraction with ether to remove starting materials afforded 4.19 gm. ofexo-cis-1,4-endoxo- 1-l({3-Cyanoethoxy)methyl] Acyclohexene-2,3-dicarboxylic anhydride.

EXAMPLE 3 Exo-cis-1,4-endoxo-1-(fi-carboxyethoxymethyl)-A-cyclohexene-Z,3dicarb0xylate, trisodium salt To a 250 ml. Erlenmeyerflask were added 9.8 gm. (0.1 mole) furfuryl alcohol and 0.1 gm. sodium.After stirring the mixture for three minutes, 9 gm. (0.105 mole) methylacrylate were slowly added with stirring. After 5-10 min. the mixturewas immersed in a water bath maintained at -70 C. The mixture was thenfractionally distilled and methyl acrylate removed in the firstfraction. The product, which distilled at 120130/23 mm. (16.5 gm.) was 2[,8 (carboxylmethoxy)ethoxymethylJ-furan.

To a 250 ml. Erlenmeyer flask fitted with condenser and drying tube wereadded 6.9 g. (0.038 mole) of the substituted furan described above, ml.anhydrous ether and 3.8 g. (0.039 mole) maleic anhydride. The mixturewas allowed to stand for three days and was then evaporated under vacuumwithout heat. The viscous liquid was shaken with an aqueous solution ofsodium carbonate which was maintained at pH-6 by addition of smallincrements of sodium carbonate. The immiscible portion was extractedwith ether, the ether fraction evaporated and the residue heated with anaqueous sodium carbonate solution maintained at pH-10 on a steam bathfor 15 min. The solution Was evaporated under vacuum with heat to afiordthe title compound.

What is claimed is:

1. Disodium exo cis 1,4-endoxo-1-[(fi'cyanoethoxy) methyl] -A-cyclohexene-2, 3 -dicarboxylate.

2. Trisodium exo-cis 1,4-endoxo-l-(fi-carboxyethoxymethyl) -A-cyclohexene-2,3-dicarboxylate.

References Cited Scarpa et al., C. A6, vol. 64 (1966), 17469e.

DONALD G. DAUS, Primary Examiner B. DENTZ, Assistant Examiner US. Cl.X.R. 25289

